CN111017991A - High-purity zirconium oxychloride extraction process - Google Patents
High-purity zirconium oxychloride extraction process Download PDFInfo
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- CN111017991A CN111017991A CN201911316647.4A CN201911316647A CN111017991A CN 111017991 A CN111017991 A CN 111017991A CN 201911316647 A CN201911316647 A CN 201911316647A CN 111017991 A CN111017991 A CN 111017991A
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- C01G25/00—Compounds of zirconium
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Abstract
The invention discloses a high-purity zirconium oxychloride extraction process, which comprises the following steps: (1) an alkali fusion process, (2) a water washing and filter pressing process, (3) a transformation process, (4) an acidification process, (5) a primary cooling crystallization process, (6) a dissolution filtration process, (7) an extraction process, (8) a concentration process, (9) a secondary crystallization process, and (10) an acid washing filtration process. The invention adds an extraction procedure after the filter pressing silicon removal procedure, extracts ferric oxide and some impurities in the clear liquid into the extractant by the extractant, thereby reducing the content of the impurities in the clear liquid, wherein the content of the ferric oxide can be controlled below 1ppm, and the impurities remained in the crystal are leached out by a leaching method, thereby reducing the content of the impurities and improving the main content of the product.
Description
Technical Field
The invention relates to a high-purity zirconium oxychloride extraction process.
Background
Zirconium oxychloride is a main raw material for manufacturing other zirconium products, and is used for products such as textiles, leather, rubber additives, metal surface treatment agents, coating drying agents, refractory materials, ceramics, catalysts, fire retardants and the like.
In recent years, with the rapid growth of nonferrous metal industry in China, the zirconium chemical industry makes great progress in the aspects of production, import and export, environmental protection, energy conservation, consumption reduction, emission reduction, scientific research application and the like, the production and the application of the zirconium chemical industry gradually develop to the high-technology field, particularly the production and the application of zirconium-based or zirconium-containing modern ceramic materials such as energy materials, optical materials, biological materials, environment-friendly materials and the like are steadily developed, and the product variety and the yield are continuously increased. China has become the largest zirconium sand import and application country in the world, and the largest zirconium oxychloride production country and export country. The annual output of chemical zirconium products such as zirconium oxychloride, zirconium carbonate, zirconium dioxide, fused zirconium, zirconium silicate and the like has exceeded 20 million tons in 2007, and the export has increased year by year, wherein zirconium oxychloride is exported to 57000 tons or more in countries such as riinmeide in 2007.
The existing alkali fusion sintering method for producing zirconium oxychloride has the outstanding problems of discontinuous alkali fusion sintering process, low production efficiency, high energy consumption, low automation level and high labor intensity; the problem of three wastes is to be solved, and a large amount of waste acid, waste alkali and waste residue are generated in the production process of zirconium oxychloride.
Disclosure of Invention
The invention aims to solve the technical problem of providing a high-purity zirconium oxychloride extraction process, which has the advantages of continuous alkali fusion sintering process, high production efficiency, full utilization of resources, effective reduction of impurity content in products and improvement of product quality. The discharge of waste acid, waste alkali and waste residue is reduced.
In order to solve the technical problems, the invention adopts the following technical means:
a high-purity zirconium oxychloride extraction process comprises the following steps:
(1) and the alkali fusion process is to add zircon sand into caustic soda flakes at the temperature of 600 ℃ and melt for 15 minutes to obtain zirconium silicate and sodium silicate:
(2) washing with water, and performing filter pressing, wherein sodium silicate is washed away by washing with water to form a sodium silicate aqueous solution which is sold as a byproduct, and zirconium silicate is washed by water and is subjected to filter pressing to form a filter cake;
(3) a transformation procedure, adding water into the filter cake obtained in the step (2), stirring the filter cake into slurry, adding mother liquor to adjust the pH value to 6.5-7.5, and then performing filter pressing to obtain a filter cake;
(4) acidifying, namely adding leacheate into the filter cake obtained in the step (3), stirring the filter cake into slurry, then pumping the slurry into the acidifying process, heating and dissolving the slurry, and then adjusting the acidity and the zirconium content, wherein the acidity of the zirconium dioxide is 220kg/l and is 7 equivalent concentration;
(5) a primary cooling crystallization process, wherein the solution in the step (4) is conveyed to a crystallization tank for natural cooling;
(6) dissolving and filtering, namely adding the acidic zirconium-containing water solution for washing the silicon slag into a crystallization tank after 72 hours in the step (5), stirring uniformly by using a stirrer, adding a flocculating agent, testing the acidity to be 4.5 equivalent concentration and the zirconium content to be 105kg/l, pumping into a pressure tank after the solution is qualified, pressurizing to 0.3MP for filter pressing, putting the clear liquid into a clear liquid storage tank, and carrying out secondary fine filtration on the clear liquid to obtain clear liquid of the silicon slag and the zirconium oxychloride solution subjected to secondary fine filtration;
(7) extracting, namely pumping clear liquid of zirconium oxychloride solution into an extraction tank, and extracting impurities by using an extractant to obtain pure clear liquid;
(8) a concentration process, namely preheating the clear liquid obtained in the step (7) in a preheating tank, and pumping the preheated clear liquid into an evaporation tank for concentration; zirconium dioxide content 210kg/l, acidity 6.8 normality;
(9) performing secondary crystallization, namely performing secondary crystallization on the concentrated solution obtained in the step (8), and naturally cooling to 35 ℃;
(10) and (4) acid washing and filtering, namely conveying the material obtained in the step (9) to a suction filtration tank, pumping the mother liquor to be dry, adding leacheate to repeatedly leach, pumping the slurry into a centrifugal machine to be centrifugally dewatered, and obtaining solid, namely crystalline zirconium oxychloride through the acid washing and filtering process.
The invention has the advantages that:
(1) adding an extraction procedure after the filter pressing silicon removal procedure, and extracting ferric oxide and some impurities in the clear liquid into the extraction agent by using the extraction agent so as to reduce the content of the impurities in the clear liquid, wherein the content of the ferric oxide can be controlled below 1 ppm.
(2) And leaching out impurities remained in the crystals by a leaching method, thereby reducing the content of the impurities and improving the main content of the product.
(3) Can produce into sodium silicate with waste lye and silicon slag, sell as the product, useless acid mother liquor water retrieves the zirconium oxychloride of inside after, retrieves the scandium oxide of the inside again, and a small amount of sewage is up to standard in the production discharges the sewage treatment plant in garden.
The further preferred technical scheme is as follows:
and (3) mixing the slag in the step (6) with the washing alkali liquor generated in the step (2) to produce anhydrous sodium metasilicate.
And (4) conveying the acid liquor obtained in the step (10) to the steps (3) and (4) for recycling the acid liquor.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples.
Referring to fig. 1, the extraction process of high purity zirconium oxychloride of the present invention comprises the following steps:
(1) and the alkali fusion process is to add zircon sand into caustic soda flakes at the temperature of 600 ℃ and melt for 15 minutes to obtain zirconium silicate and sodium silicate:
(2) washing with water, and performing filter pressing, wherein sodium silicate is washed away by washing with water to form a sodium silicate aqueous solution which is sold as a byproduct, and zirconium silicate is washed by water and is subjected to filter pressing to form a filter cake;
(3) a transformation procedure, adding water into the filter cake obtained in the step (2), stirring the filter cake into slurry, adding mother liquor to adjust the pH value to 6.5-7.5, and then performing filter pressing to obtain a filter cake;
(4) acidifying, namely adding leacheate into the filter cake obtained in the step (3), stirring the filter cake into slurry, then pumping the slurry into the acidifying process, heating and dissolving the slurry, and then adjusting the acidity and the zirconium content, wherein the acidity of the zirconium dioxide is 220kg/l and is 7 equivalent concentration;
(5) a primary cooling crystallization process, wherein the solution in the step (4) is conveyed to a crystallization tank for natural cooling;
(6) dissolving and filtering, namely adding the acidic zirconium-containing water solution for washing the silicon slag into a crystallization tank after 72 hours in the step (5), stirring uniformly by using a stirrer, adding a flocculating agent, testing the acidity to be 4.5 equivalent concentration and the zirconium content to be 105kg/l, pumping into a pressure tank after the solution is qualified, pressurizing to 0.3MP for filter pressing, putting the clear liquid into a clear liquid storage tank, and carrying out secondary fine filtration on the clear liquid to obtain clear liquid of the silicon slag and the zirconium oxychloride solution subjected to secondary fine filtration;
(7) extracting, namely pumping clear liquid of zirconium oxychloride solution into an extraction tank, and extracting impurities by using an extractant to obtain pure clear liquid;
(8) a concentration process, namely preheating the clear liquid obtained in the step (7) in a preheating tank, and pumping the preheated clear liquid into an evaporation tank for concentration; zirconium dioxide content 210kg/l, acidity 6.8 normality;
(9) performing secondary crystallization, namely performing secondary crystallization on the concentrated solution obtained in the step (8), and naturally cooling to 35 ℃;
(10) and (4) acid washing and filtering, namely conveying the material obtained in the step (9) to a suction filtration tank, pumping the mother liquor to be dry, adding leacheate to repeatedly leach, pumping the slurry into a centrifugal machine to be centrifugally dewatered, and obtaining solid, namely crystalline zirconium oxychloride through the acid washing and filtering process.
The advantages of this embodiment are:
(1) adding an extraction procedure after the filter pressing silicon removal procedure, and extracting ferric oxide and some impurities in the clear liquid into the extraction agent by using the extraction agent so as to reduce the content of the impurities in the clear liquid, wherein the content of the ferric oxide can be controlled below 1 ppm.
(2) And leaching out impurities remained in the crystals by a leaching method, thereby reducing the content of the impurities and improving the main content of the product.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the scope of the present invention, which is defined in the appended claims.
Claims (3)
1. The extraction process of the high-purity zirconium oxychloride is characterized by comprising the following steps of:
(1) the alkali fusion process is to add zircon sand into caustic soda flakes at 600 ℃ and melt for 15 minutes to obtain zirconium silicate and sodium silicate;
(2) washing with water, and performing filter pressing, wherein sodium silicate is washed away by washing with water to form a sodium silicate aqueous solution which is sold as a byproduct, and zirconium silicate is washed by water and is subjected to filter pressing to form a filter cake;
(3) a transformation procedure, adding water into the filter cake obtained in the step (2), stirring the filter cake into slurry, adding mother liquor to adjust the pH value to 6.5-7.5, and then performing filter pressing to obtain a filter cake;
(4) acidifying, namely adding leacheate into the filter cake obtained in the step (3), stirring the filter cake into slurry, then pumping the slurry into the acidifying process, heating and dissolving the slurry, and then adjusting the acidity and the zirconium content, wherein the acidity of the zirconium dioxide is 220kg/l and is 7 equivalent concentration;
(5) a primary cooling crystallization process, wherein the solution in the step (4) is conveyed to a crystallization tank for natural cooling;
(6) dissolving and filtering, namely adding the acidic zirconium-containing water solution for washing the silicon slag into a crystallization tank after 72 hours in the step (5), stirring uniformly by using a stirrer, adding a flocculating agent, testing the acidity to 4.5 equivalent concentration, testing the zirconium content to 105kg/l, pumping into a pressure tank after the zirconium content is qualified, pressurizing and filter-pressing, putting the clear liquid into a clear liquid storage tank, and carrying out secondary fine filtration on the clear liquid to obtain clear liquid of the silicon slag and the zirconium oxychloride solution subjected to secondary fine filtration;
(7) extracting, namely pumping clear liquid of zirconium oxychloride solution into an extraction tank, and extracting impurities by using an extractant to obtain pure clear liquid;
(8) a concentration process, namely preheating the clear liquid obtained in the step (7) in a preheating tank, and pumping the preheated clear liquid into an evaporation tank for concentration; zirconium dioxide content 210kg/l, acidity 6.8 normality;
(9) performing secondary crystallization, namely performing secondary crystallization on the concentrated solution obtained in the step (8), and naturally cooling to 35 ℃;
(10) and (4) acid washing and filtering, namely conveying the material obtained in the step (9) to a suction filtration tank, pumping the mother liquor to be dry, adding leacheate to repeatedly leach, pumping the slurry into a centrifugal machine to be centrifugally dewatered, and obtaining solid, namely crystalline zirconium oxychloride through the acid washing and filtering process.
2. The process of claim 1, wherein the extraction of zirconium oxychloride is carried out in the presence of a solvent, wherein: and (3) mixing the slag in the step (6) with the washing alkali liquor generated in the step (2) to produce anhydrous sodium metasilicate.
3. The process of claim 1, wherein the extraction of zirconium oxychloride is carried out in the presence of a solvent, wherein: and (4) conveying the acid liquor obtained in the step (10) to the steps (3) and (4) for recycling the acid liquor.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115469620A (en) * | 2022-09-16 | 2022-12-13 | 金业新材料科技(昆山)有限公司 | Intelligent control device, method, system and medium for zirconia powder production |
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| CN104003439A (en) * | 2013-02-26 | 2014-08-27 | 中国科学院过程工程研究所 | Method for preparing zirconium oxychloride solution |
| CN104003441A (en) * | 2013-02-26 | 2014-08-27 | 中国科学院过程工程研究所 | Method for desiliconization by hydrochloric acid decomposition during alkali fusion process zirconium oxychloride production |
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Application publication date: 20200417 |